US005934577A

Ulllted States Patent [19] [11] Patent Number: 5,934,577

Vandenhende et al. [45] Date of Patent: Aug. 10, 1999

[54] PROCESS FOR SEPARATING THE FOREIGN PATENT DOCUMENTS

CONSTITUENTS OF A MUTLILAYER
MATERIAL 0581089 2/1994 European Pat. Off. .
0587005 3/1994 European Pat. Off. .
[75] Inventors: Bernard Vandenhende, Leest; 4225977 1/1994 Germany '
J ean-Marie YernauX, Rixensart, both 08238440 9/1996 Japan '
of Belgium
Primary ExaminerMark Rosenbaum
[73] Asslgneei solvay (Soclete Anonyme) Brussels Attorney, Agent, or FirmVenable; George H. Spencer;
Belglum John W. Schneller

[21] Appl. No.: 08/972,952 [57] ABSTRACT

[22] Flled: NOV 19 1997 Process for separating the constituents of a multilayer mate
[30] Foreign Application priority Data rial including at least one layer of a base plastic (A) and a
_ layer of a plastic (B) Which are separated by a layer of
Jul. 11, 1997 [BE] Belgium ............................. .. 09700611 adhesive plastic (C), in Which: (1) the material is heated to
[51] Int. Cl? ................................................... .. 1302c 19/12 a temperature T1 between the Crystallization temperature of
[52] US. Cl. .......................................... .. 241/23; 241/2428 the Plastic B (TC) and TC20 C~> (2) the material is next
[58] Field of Search ....................... .. 156/344 241/2418 Shredded by being Subjected to Shearing at aPPrX.imate1y
241/2428 23 24 14_ 209/3 the same temperature, so as to produce delamination and
' thus to convert the material into particles of small dimen
[56] References Cited sions of tWo types, some consisting essentially of base
plastic (A) and others (Y) consisting essentially of plastic B
U.S. PATENT DOCUMENTS and of adhesive plastic (C), and (3) the particles X and Y are
471997109 4/1980 Watanabe ' subsequently separated by electrostatic separation.
4,775,697 10/1988 Schoenhard .
5,366,091 11/1994 Stahl et al. . 14 Claims, N0 Drawings
 5,934,577
1 2
PROCESS FOR SEPARATING THE
CONSTITUENTS OF A MUTLILAYER
MATERIAL
FIELD OF THE INVENTION
The present invention relates to the recycling of multi
layer materials based on plastics. It relates more particularly
to the separation of the constituents of a multilayer material
including at least one layer of a base plastic and a layer of
a barrier plastic Which are separated by a layer of adhesive
plastic.
TECHNOLOGY REVIEW
Such multilayer materials are commonly employed in
very diverse industries, for example in the manufacture of
packaging materials or of fuel tanks. An example of a
multilayer fuel tank comprises 5 layers: PE/adhesive/
EVOH/adhesive/PE, Where PE denotes high density poly
ethylene and EVOH denotes an ethylene-vinyl alcohol
copolymer, it being possible for the adhesive to be especially
a polyethylene grafted With maleic anhydride (PE-g-MA).
SUMMARY OF THE INVENTION
During the manufacture of plastics-based articles, espe
cially by bloW extrusion, a large quantity of scrap is
unavoidably produced (often more than 40%), the recovery
of Which is economically advantageous. The same is even
more the case Where Whole substandard articles are rejected.
In the case of multilayer materials the presence of several
different plastics sometimes presents problems: if it is
deemed sufficient to grind the multilayer material into
particles and to reemploy them in the manufacture of a neW
article, the latter runs the risk of exhibiting mediocre
mechanical performance and therefore the quantities of
material thus recycled must be greatly restricted. It is
therefore desirable to have available a simple and effective
method enabling the constituents of multilayer materials to
be separated With a vieW to being able to reemploy them in
a manner Which is comparable With virgin constituents,
Without affecting the performance of the neW articles manu
factured from constituents Which are thus recovered.
Anumber of methods have already been proposed for this
purpose. It is thus especially knoWn to immerse multilayer
materials in appropriate organic solvents (for example
xylene) at elevated temperature, With a vieW to separating
some constituents by selective dissolving. HoWever, such a
method requires the use of organic solvents, Which are costly
and generally present safety and environmental problems,
and a subsequent drying Which is costly in energy. In
addition, even if the temperature of the solvent is raised,
treatment periods of more than an hour are commonplace.
These disadvantages are particularly marked When the
articles to be treated are thick, for example fragments of fuel
tanks. This is because a preliminary optional grinding gen
erally does not make it possible to reduce the thickness of
the particles obtained, and this is detrimental to the rate at
Which they dissolve. Such a solution is therefore not suited
to the treatment of large quantities of material.
Consequently, the present invention aims to provide a
process Which is simple, fast and efficient, and Which does
not require large quantities of solvents to be employed.
DETAILED DESCRIPTION OF THE
INVENTION
To this end the present invention relates to a process for
separating the constituents of a multilayer material including
at least one layer of a base plastic (A) and a layer of a plastic
(B) Which are separated by a layer of adhesive plastic (C),
in Which:
(1) the material is heated to a temperature T1 betWeen the
crystalliZation temperature of the plastic B (Tc) and
Tc20 C.,
(2) the material is then shredded by being subjected to
shearing, at approximately the same temperature, so as
to produce delamination and thus to convert the mate
10 rial into particles of small dimensions of tWo types,
some consisting essentially of base plastic (A) and
others (Y) consisting essentially of plastic B and of
adhesive plastic (C), and
(3) the particles X and Y are subsequently separated by
electrostatic separation.
Plastic is intended to denote any polymer or polymer
mixture. The polymers in question are preferably thermo
plastic. Each of the plastics (A, B, C) may in addition
optionally contain one or several conventional additives
such as stabiliZers, lubricants, antioxidants, pigments, ?ame
retardants, ?llers or reinforcing ?llers, and the like.
Good results have been obtained When the base plastic
(A) represents more than 80% of the total Weight of the
plastics A, B and C, and in particular more than 90%.
The base plastic (A) is chosen as a function of the
mechanical and/or chemical properties Which the material
must have. Conventional polymers such as polyole?ns or
vinyl chloride polymers are generally employed for this
purpose. The process according to the invention gives good
results When the base plastic (A) consists essentially of one
or more polyole?ns chosen from the homopolymers and
copolymers of ethylene or of propylene, and in particular of
high density polyethylene (HDPE).
The process according to the invention is found to be
particularly advantageous and ef?cacious When the plastic B
is a barrier plastic. Abarrier plastic is intended to denote any
plastic capable of forming a layer exhibiting a loW perme
ability to particular ?uids such as, for example,
hydrocarbon-based fuels. Advantageous crystalline poly
mers Which have such properties are especially polyamides,
?uorine-containing polymers and ethylene-vinyl alcohol
copolymers. The process according to the invention gives
very good results When the plastic B consists essentially of
one or more polymers chosen from polyamides and
ethylene-vinyl alcohol copolymers, and very particularly of
the latter. Plastic B often has a loW adhesiveness to the
conventional polymers of Which the layer of base plastic
generally essentially consists, and this often makes it nec
essary to resort to an adhesive plastic
50 The adhesive plastic (C) is chosen as a function of the
nature of the plastics A and B. A compatibiliZed polyole?n,
and in particular compatibiliZed polyethylene is frequently
employed as adhesive plastic The compatibiliZation can
be obtained especially by grafting, in particular by means of
a carboxylic acid anhydride, for example maleic anhydride.
The adhesive plastic (C) preferably consists essentially of a
polyole?n grafted With maleic anhydride, in particular poly
ethylene or polypropylene grafted With maleic anhydride.
When the base plastic (A) consists essentially of polyethyl
aO ene or of polypropylene the adhesive plastic (C) is advan
tageously a grafted polymer of the same kind (PE or PP
respectively).
Besides the abovementioned 3 layers A/C/B the multi
layer material subjected to the process according to the
5 invention may optionally include one or more other layers of
identical or different nature. It may thus involve especially
a material of symmetrical structure A1/C1/B/C2/A2, A1 and
 5,934,577
3 4
A2 denoting layers of base plastics Which are identical or
different (in nature as in thickness), and C1 and C2 denoting
layers of adhesive plastics Which are identical or different. It
may further involve an asymmetric structure, for example of
the A1/C/B/C/A2/A1 type. Another example is that of a
material comprising several barrier layers, such as A/C/B/
C/A/C/B.
Before the abovementioned stage (1) the process accord
ing to the invention may optionally include one or more
conventional stages such as, for example, Washing, or else
chopping at ambient temperature, intended to reduce the
material to fragments of medium dimensions (for example
of the order of a feW centimetres).
The heating (1) can be carried out by any knoWn means,
for example by means of lamps or resistances emitting
infrared radiation. The purpose of this heating is to bring the
material to a temperature Which is suitable With a vieW to
shredding
Stage (2) of the process according to the invention con
sists in shredding the multilayer material at a speci?c
temperature. Surprisingly, it has been found that the fact of
subjecting the multilayer material to shearing forces at a
temperature slightly loWer than the crystalliZation tempera
ture of the plastic B makes it possible to effect the separation
of, on the one hand, A and, on the other hand B+C. It Will
be noted that the separation thus produced is original, insofar
as the conventional methods of recycling multilayer mate
rials comprising a barrier plastic have the objective of
recovering the latter and otherWise yield a generally large
quantity of a mixture of base plastic and of adhesive plastic,
Which is aWkWard to reexploit directly. In other Words, an
important characteristic of the process according to the
invention is that it is a process Which makes it possible to
separate the base plastic from the other plastics. This is
particularly advantageous insofar as, in the majority of
cases, the base plastic (A) represents the mainvconstituent of
the material by Weight. Its recovery is therefore economi
cally important. In fact, even though the barrier plastic is
often more costly, it often represents only a small percentage
of the total Weight of the material. Thus, in the case of the
5 -layer fuel tank described in the introduction, the Weight of
EVOH is generally of the order of 3 to 4% relative to the
total Weight of the tank.
Another advantage of the process according to the inven
tion is that it can take place in relatively simple equipment,
Which must, nevertheless, permit the temperature of its
contents to be precisely controlled. The material is prefer
ably shredded in an impeller mill. This type of equipment is
Well knoWn as such; it generally consists of a rotary drum
provided With blades at its periphery, rotating in a vessel to
Which blades are also secured. Amodel capable of producing
particles from approximately 5 to 12 mm in siZe is generally
chosen, these speci?c dimensions making it possible to
perform the separation With a high efficiency. It is further
more advantageous that the knife blades With Which the mill
is provided should not be too cutting, otherWise the materials
Would be cut up Without being subjected to signi?cant
shearing forces.
The equipment employed for the shredding (2) is prefer
ably used in combination With means for thermal condition
ing Which make it possible to maintain the temperature
therein Within the abovementioned range. In general, the
shredding produces additional heating of the material, With
the result that it is often useful to cool the latter, for example
With a stream of air at ambient temperature, in order to avoid
clustering of the shredded particles. The same device is
advantageously employed for cooling the particles and for
removing them, by suction, out of the shredder.
Similarly, before carrying out the electrostatic separation
(3) it may be useful to remove the ?nes :(microparticles)
produced by the shredding; a conventional device such as an
air classi?er may be employed for this purpose.
The separation (3) of the particles X and Y is performed
by electrostatic separation.
Within the electrostatic separation stage a ?rst substage
consists in charging the particles, for example by corona
discharge or else by subjecting them to friction. This may
involve mutual friction, for example in a ?uidiZed bed, or
else friction of the particles on a moving member (drum, belt
or the like) of an appropriate nature (glass, plastic, or the
like).
It is advantageous that after the shredding (2) the particles
15 should be charged electrically, With a vieW to electrostatic
separation, at a temperature (T3) of at least 50 C. In order
to bring the particles into this temperature rangeif they are
not yet in itit is possible in particular to employ a
conventional heating device such as an infrared lamp. It is
also possible advantageously to employ a charging equip
ment provided With heating elements such as electrical
resistances. It has been found that When the charging of the
particles Was thus carried out at an elevated temperature, the
selectivity of the subsequent electrostatic separation could
25 be surprisingly improved. An advantage of this alternative
method, in the context of the Whole process according to the
invention, is that at the end of the shredding (2) the particles
are already at an elevated temperature, and this signi?cantly
reduces the energy required for the abovementioned heating,
as Well as the duration of this heating. Another advantage of
this alternative method is that it alloWs the actual electro
static separation to be performed With heating, and this has
been found advantageous in the present context.
It is furthermore desirable that the substage of charging
35 the particles should take place in an atmosphere of the
loWest possible humidity. For this purpose a gas Which has
a loW moisture content, for example dry air or an inert gas
such as nitrogen, may in particular be injected into the
charging equipment employed.
According to an alternative form Which has been found
advantageous in this context, after the shredding (2) the
particles to be separated are charged electrically by being
brought into contact With a movable member consisting
essentially, at least super?cially, of a plastic similar to the
45 adhesive plastic Aplastic similar to the adhesive plastic
(C) is intended to denote a plastic Which exhibits similar
triboelectric characteristics. The surface of the movable
member preferably consists of a plastic identical With the
adhesive plastic
According to another advantageous alternative form,
Which may be combined With the preceding one, the par
ticles to be separated are charged electrically by passing
through a holloW rotary drum provided internally With
components Which are approximately perpendicular to its
55 internal surface. Such components make it possible to inten
sify the friction of the particles on the internal surface of the
drum, and this increases their electric charge. Examples of
such components Which may be employed are one or more
rods, small plates and/or paddles Which are approximately
parallel to the axis of the drum. The drum is advantageously
cylindrical in shape; it may, hoWever, have a section other
than circular, for example polygonal, in particular octagonal.
The axis of the drum may be horiZontal or slightly inclined
so as to make it easier for the particles to travel forWard from
65 one end to the other. The angle of inclination and the speed
of rotation of the drum alloW the residence time of the
particles Within it to be adjusted.
 5,934,577
5 6
Once they have been electrically charged, the particles
can be easily separated, in a manner known per se, by falling
betWeen tWo de?ecting electrodes exhibiting a continuous
and high potential difference. According to a preferred
alternative form the actual separation is performed by depos
iting the precharged particles on the external surface of a
rotary drum Whose axis is horiZontal and Which is connected
to a terminal of a DC voltage source, the other terminal
thereof being connected to a de?ecting electrode consisting,
for example, of a planar plate placed on the side of the said
drum, parallel to its axis, generally at a distance of a feW
centimetres. In this Way the particles carrying an electric
charge of opposite sign to the de?ecting electrode Will be
diverted toWards the latter on falling from the drum, and this
alloWs the particles to be separated according to their charge
and hence according to their nature. It is preferred that the
drum in question should at least super?cially consist of an
insulating material, for example of PVC, its internal surface
being provided With electrically conductive means or coat
ing ensuring a homogeneous distribution of the electric
charges. The use of an insulating drum alloWs high electric
?elds to be obtained, of the order of 3 to 15 kV/cm, in
contrast to the knoWn processes employing a conductive
drum, With Which the electric ?eld cannot exceed 2 or 3
kV/cm Without leading to a risk of breakdoWn. In the 25
process according to the invention, When employing an
insulated separating drum, ?elds of 6 to 8 kV/cm have given
very good results.
The electrostatic separation is preferably performed With
heating, the particles being at a temperature of at least 50
C.
After separation of the particles X and Y the particles Y
are advantageously subjected to a subsequent stage (4) of
separation making it possible to collect, on the one hand, the
plastic B and, on the other hand, the adhesive plastic To
give an example, if the plastic B consists of EVOH, it can
be recovered by dissolving the Y particles in a Water/alcohol
solution, preferably With heating (for example a Water/
methanol mixture at 70 C.).
The present invention also relates to a process for recy
cling fuel tanks including at least one layer of a base plastic
(A) and a layer of a barrier plastic (B) Which are separated
by a layer of adhesive plastic (C), or fragments of such
tanks, in Which the tanks or tank fragments are subjected to
the process of separation de?ned above. As already
indicated, this process can be applied particularly Well to
tanks in Which the layer(s) of barrier plastic (B) consists
(consist) essentially of EVOH, the layer(s) of adhesive
plastic (C) consisting essentially of PE-g-MA.
EXAMPLE
Fragments of fuel tanks With 5 layers of the HDPE/PE
g-MA/EVOH/PE-g-MA/HDPE type Were subjected to the
process according to the invention. These fragments, the
mean length of Which Was of the order of 10 to 20 cm, Were 55
?rst heated to approximately 150 C. and then shredded in
an impeller mill (of Rapidtrademark, model 3026), at the
same temperature. The particles thus obtained, of a mean
siZe of approximately 8 mm, Were next charged electrically
by passing through a holloW rotary drum (length: 100 cm,
internal diameter: 40 cm, speed of rotation: 30 to 70 rev/
min) arranged horiZontally, the internal Wall of Which Was
coated With PE-g-MA. The mean temperature Within the
drum Was approximately 80 C. On leaving this ?rst drum
the particles Were deposited on the upper generatrix of a
second rotary drum, made of PVC (diameter: 40 cm, length:
40 cm, thickness: 10 mm, speed of rotation: 15 to 50
rev/min), the axis of Which Was arranged horiZontally and
perpendicularly to that of the ?rst drum. A source of DC
voltage (70 kV) Was connected, on the one hand, to the metal
coating applied to the internal surface of the second drum
and, on the other hand, to a metal plate placed laterally
facing the second drum, at a distance of 3 to 8 cm.
A number of trials Were carried out, With mean particle
throughputs of 30 to 120 kg/h.
The separation thus produced made it possible to collect,
on the one hand, HDPE particles and, on the other hand,
particles of EVOH/PE-g-MA mixture, and to do this With an
excellent selectivity, since the HDPE thus recovered exhib
15 ited a purity of more than 99.5% by Weight.
What is claimed is:
1. Aprocess for separating the constituents of a multilayer
material including at least one layer of a base plastic (A) and
a layer of a plastic (B) Which are separated by a layer of
adhesive plastic (C), comprising steps for:
(1) heating the material to a temperature T1 betWeen the
crystalliZation temperature of the plastic B (Tc) and
Tc20 C.,
(2) shredding the material by subjecting the material to
shearing, at approximately the same temperature, so as
to produce delamination and thus to convert the mate
rial into particles of small dimensions of tWo types,
some consisting essentially of base plastic (A) and
others (Y) consisting essentially of plastic (B) and of
adhesive plastic (C), and
(3) separating the particles X and Y by electrostatic
separation.
35
2. The process according to claim 1, in Which the base
plastic (A) consists essentially of one or more polyole?ns
chosen from the homopolymers and copolymers of ethylene
or of propylene.
3. The process according to claim 1, in Which the plastic
B is a barrier plastic.
4. The process according to claim 1, in Which the plastic
B consists essentially of one or more polymers chosen from
polyamides and ethylene-vinyl alcohol copolymers.
45 5. The process according to claim 1, in Which the adhesive
plastic (C) consists essentially of a polyole?n grafted With
maleic anhydride.
6. The process according to claim 1, in Which, after the
shredding (2), the particles are charged electrically, With a
vieW to electrostatic separation, at a temperature (T3) of at
least 50 C.
7. The process according to claim 1, in Which, after the
shredding (2), the particles to be separated are charged
electrically by being brought into contact With a movable
member having a surface consisting essentially of a plastic
similar to the adhesive plastic
8. The process according to claim 1, in Which the particles
to be separated are charged electrically by passing through
a holloW rotary drum provided internally With components
Which are approximately perpendicular to its internal sur
face.
9. The process according to claim 1, in Which, after
separation of the particles X and Y, the particles Y are
65 subjected to a subsequent stage (4) of separation making it
possible to collect, on the one hand, the plastic B and, on the
other hand, the adhesive plastic
 5,934,577
7 8
10. The process according to claim 1 wherein said mul some consisting essentially of base plastic (A) and
tilayer material is a fuel tank or fragment of said tank others (Y) consisting essentially of plastic (B) and of
including at least one layer of a base plastic (A) and a layer adhesive plastic (C), and
of a barrier plastic (B) Which are separated by a layer of
adhesive plastic 5
(3) separating the particles X and Y by electrostatic
11. A process for recycling a fuel tank or fragment of a separation.
fuel tank, including at least one layer of a base plastic (A) 12. The process according to claim 11, in Which the base
and a layer of a barrier plastic (B) Which are separated by a plastic (A) consists essentially of one or more polyole?ns
layer of adhesive plastic (C), said base plastic (A) repre chosen from the homopolymers and copolymers of ethylene
senting more than 80% of the total Weight of plastics (A), 10 or of propylene.
(B), and (C), comprising steps for: 13. The process according to claim 11, in Which the plastic
(1) heating the material to a temperature T1 betWeen the B consists essentially of one or more polymers chosen from
crystalliZation temperature of the plastic B (Tc) and polyamides and ethylene-vinyl alcohol copolymers.
Tc20 C., 14. The process according to claim 11, in Which the
(2) shredding the material by subjecting the material to 15 adhesive plastic (C) consists essentially of a polyole?n
shearing, at approximately the same temperature, so as grafted With maleic anhydride.
to produce delamination and thus to convert the mate
rial into particles of small dimensions of tWo types, * * * * *